Coloring live human hair with water-soluble colored polymers

ABSTRACT

The method of coloring human hair with compositions which contain a dissolved water-soluble film forming polymer that has chemically bonded dye groups. Hair dye compositions containing specific dissolved polymers that have lateral side chains chemically bonded to the polymer chain and a terminal dye group.

United States Patent [72} Inventor GregolreKaloplssis Sept. 6, 1965, Luxembourg, No. 49.441; May 13, 1965, Luxembourg, No. 48.591 Continuation-impart 01 application Ser. No. 227,542, Oct. 1, 1962, now abandoned. I

[54] COLORING LIVE HUMAN HAIR WITH WATER- SOLUBLE COLORED POLYMERS 27 Claims, No Drawings [52] U.S.CI 8/10.1. 8/10. 8/79, 260/33.=4, 260/33.8, 260/8072, 260/8075, 260/8076, 260/808. 424/47, 424/71 s1 1nt.C1 Al1k7/12 {so} FieldotSearch 167/88, 87.2, 87.1 260/8075, 80.76, 80.8, 80.72; 424/71, 47;8/10.1,10,79

[56] Reterences Cited UNITED STATES PATENTS 2,632,004 3/1953 Minsk et a1. 260/152 2,732,382 1/1956 Minsk et a1. 260/152 X 3,251,743 5/1966 Hahn et all 167/88 3,364.186 1/1968 Wilhelm et a1 260/8075 X Primary Exuminer-Albert T. Meyers Assirlunl Examiner-Vera C. Clarke Attorney-Holcombe, Wethcrill & Brisebois ABSTRACT: The method of coloring human hair with compositions which contain a dissolved water-soluble film forming polymer that has chemically bonded dye groups. Hair dye compositions containing specific dissolved polymers that have lateral side chains chemically bonded to the polymer chain and a terminal dye group.

COLORING LIVE HUMAN HAIR WITH WATER- SOLUBLE COLORED POLYMERS This application is a continuation-in-part of prior application Ser. No. 227,542, filed Oct. 1, 1962 now abandoned.

This invention relates to polymeric substances and to hair coloring compositions comprising the same.

Most of the lacquers or setting lotions heretofore used are transparent, and are intended to keep the hair in place while imparting certain additional qualities such as sheen or luster, without changing the color, or even the shade of the hair.

it has, however, also been suggested that hair lacquers or setting lotions be used which do affect the color of the hair to which they are applied.

It was first suggested that dyes be incorporated into the lacquers or lotions which are soluble in the solutions of resins from which they are made, but these attempts did not give satisfactory results because the dye is not adequately retained by the resin and hair treated therewith stains the skin, and any clothing coming in contact therewith.

in order to at least partially overcome this difi'rculty, it is now suggested that the lacquers or setting lotions be made with colored polymers which may be obtained by copolymerization with a colored monomer and a colorless monomer or by chemically bonding to an already polymerized resin, dyes which are capable of imparting a durable color thereto.

It has been proposed to color the hair in such manner that the duration of the dyeing effect on the hair coincides with the frequency of shampooing. One of these coloring processes is based on the use of solutions or dispersions of coloring substances in solutions, e.g. aqueous alcoholic solutions, of polymeric products which, after evaporation of the solvent in which the polymers have been dissolved, leave on each hair a film of the colored polymer. This film is water soluble so that when the hair is shampooed, the deposit of polymer is dissolved away, so removing the initial dyeing effect imparted to the hair. in this process the solutions may be applied as such or in the form of aerosols.

The foregoing process has a number of disadvantages. Thus, the coloring products so brought into solution or dispersed in the polymers may exhibit some affinity for the hair itself so that an incipient dyeing of the hair itself will occur. Moreover, the solubility of the coloring substances in the medium of the polymer is not always very good and where resort is made to the use of dispersions there is risk of the coloring substance separating out. Furthermore, there is often a lack of stability of such coloring substances in the solution in which they are employed, especially at the low concentrations in which they are used.

Moreover, it is equally well known to condense alcohols on polymers obtained by copolymerization of maleic anhydride and an unsaturated monomer to produce colorless hair lacquers.

It is equally well known to condense dyes on such polymers to obtain colored pigments which may be used in color photography.

However, it should be noted that it is not possible to obtain colored polymers suitable for use in cosmetics by mixing such colorless resins and the colored copolymers which have been devised to use in the photographic industry because the mixture of these polymers is not soluble in the alcoholic or hydroalcoholic solutions used in the cosmetic field even when they comprise only a relatively small percentage of colored polymers.

Hair lacquers or lotions must have certain contradictory qualities which are difficult to reconcile.

In the first place, these resins must be soluble in an alcoholic medium so that they may be applied and must be easily removable by simply shampooing the hair. On the other hand, they must have an excellent resistance to humidity so as to avoid giving the hair a sticky appearance, which is considered particularly unattractive.

Moreover, these resins must be sufficiently hard and transparent to impart a sheen to the hair. They must also be removable by simple brushing, but without any tendency to peel off or crumble when the hair is subjected to the bending to which a coiffure is normally subjected.

It is an object of the present invention to provide new polymeric substances and hair coloring compositions comprising the same by the use of which the foregoing disadvantages may be avoided.

It is a further object of this invention to provide colored resins having characteristics which make it possible to prepare lacquers and setting lotions which have cosmetic properties comparable to those of the best colorless lacquers actually on the market and in which the dye is bonded to the resin without adversely affecting the shade of the dye and without changing the qualities of the resin.

According to a first feature of the present invention, there are provided polymeric substances which contain acid amide groups in which the amide nitrogen atom carries an amino aryl substituent.

According to a further feature of the present invention, there are provided hair coloring compositions which comprise solutions of polymeric substances as aforesaid.

The characteristic grouping of the polymers of this invention is the grouping:

IR! -C ONRNH R where R is a substituted or nonsubstituted aryl group, R and R being a hydrogen atom or a substituted or nonsubstituted alkyl group. The polymers are thus amides formed with the aid of the aromatic diamines:

wherein R, R and R have the above-mentioned meanings, which are colored substances. Preferred polymers according to the invention have the characteristic structure:

where R' is a hydrogen atom or a methyl grouping, n is a large integer lying within the range of ll to 110, R, R, R" having the above mentioned meanings. Preferably at least 10 percent of the acid amide groups are substituted as indicated and up to percent may be so substituted.

Since the color-imparting groups are chemically part of the new polymeric materials migration of the color into the hair is avoided. Moreover, the new basic hair coloring compositions are of improved stability. it has surprisingly been observed, from the absorption spectrum of the colored polymers, that the color due to the aromatic diamine moiety is not affected by the chemical linkage of the diamine to the polymer molecule.

The colored polymers of the present invention may be produced by reacting an aromatic diamine comprising one or two primary or secondary amine groups with a polymer comprising said halide functions of the formula COX, in which X denotes a halogen, the reaction being effected in the presence of an agent assisting the elimination of hydrogen halide from the reactants.

In a preferred procedure for carrying out the process for the preparation of the colored polymers of the invention, there is employed as the starting polymer. a compound of the general formula:

-CIl;-C R') i cox in which R' has the preceding meaning, X is a halogen atom and n is a high integer such that the molecular weight is between 1,000' and l0,000. Polyacryl chloride has a unit molecular weight of 90.5. Therefore, n lies within the range of ll to l 10.

A polymer particularly suitable for carrying out the process of preparation according to the invention is polyacryl chloride, of the formula:

in which n represents a high integer within the range of l l to 1 l0. It is readily obtained by polymerizing acrylyl chloride in the presence of a, a-azo-bis-isobutyronitrile as polymerization catalyst.

Suitable aromatic diamines for reaction with the aforesaid polymer starting materials are, for example, nitroparaphenylenediamine, l-methylamino-2-nitro-4-aminobenzene. lrnethylamino-2-nitro-4-(Bdiethylaminoethyl )aminobenzene. l-nitro-3-amino-4-(B-diethylaminoethyl)aminobenzene, and I,4-diaminoanthraquinone, and a wide range of others may also be employed.

it is preferred to carry out the reaction for the preparation of the colored polymers in a medium of anhydrous dioxane.

It may be noted that, in the condensation of polyacryl chloride with the aforesaid amines, the reactive groups do not necessarily all react for various reasons, such as. for example, steric hindrance or slight hydrolysis of the acid chloride function. This is apparent from the fact that the percentage of nitrogen found in the case of the colored polymers is often lower than the percentage of nitrogen as calculated from the knowledge of the starting materials.

The hair coloring compositions according to the invention may consist simply of solutions of the colored polymeric materials or may contain additionally other polymers, as desired. Thus, in order to increase the plasticity of the film by which the hairs are coated, and the water solubility so as to facilitate elimination, the colored polymers may be mixed, for example, with polyvinylpyrrolidone or other polymers usually employed in the capillary art.

The following examples will serve to illustrate the invention:

EXAMPLE 1 50 g. of polyacryl chloride are dissolved in 1 liter of anhydrous dioxane and there is then added drop-by-drop, at room temperature, a solution of 190 g. of nitroparaphenylene diamine in L9 liters of dioxane, the said solution also containing triethylamine in a proportion of 44 g./l., intended to combine with the hydrochloric acid liberated in the course of the reaction.

The molar ratio of amine to chloride grouping in the reac tion mixture is thus 1.5 and the molar ratio of triethylamine to chloride grouping is l.

The mixture is allowed to stand for 48 hours at room temperature and the precipitate formed is then separated, washed with dioxane to remove any excess of uncondensed amine and then washed with boiling water to remove the triethylamine hydrochloride formed. The polymer obtained, which has the following formula:

in which n is a high integer. is thereafter dried in vacuo. Analysis gives;

C alculaled Found which corresponds to a condensation yield of 78 percent.

EXAMPLE 2 Polyacryl chloride is reacted with l-methylamino-2-nitro-4- aminobenzene under the conditions described in example I, the molar ratio of amine to chloride grouping being L5 and the molar ratio of triethylamine to chloride grouping being 1. Analysis of the resulting colored polymer gives:

C alculaled Found which corresponds to a condensation yield of 83 percent.

EXAMPLE 3 Calculated l'LSU Found which corresponds to a condensation yield of 85 percent.

EXAMPLE 4 Polyacrylyl chloride is reacted with l-nitro-3amino-4-(B- diethylaminoethyl)aminobenzene under the conditions described in example i, the molar ratio of amine to chloride grouping being L5 and the molar ratio of triethylamine to chloride grouping being 1.

Analysis of the colored polymer gives:

Calculated Found which corresponds to a condensation yield of 59 percent.

EXAMPLE 5 Polyacrylyl chloride is reacted with l,4-diaminoanthraquinone under the conditions described in example I, the molar ratio of amine to chloride grouping being 1.5 and the molar ratio of triethylamine to chloride grouping being 1.

Analysis of the colored polymer obtained gives:

Calculated ll I Found The percentage of nitrogen found in the case of this colored polymer is higher than that calculated.

EXAMPLE 6 The following mixture is prepared:

(olored polymer ol'cxumplc 5 0.! 3, Alcohol qs. for lUO cc.

To 20 parts of this mixture are added 50 parts of "Freon l l," trichlorofluromethane and 30 parts of Freon l2," dichlorodifluoromethane. This mixture, sprayed onto white hair, leaves, on drying, a mauve color. This color disappears completely on washing the hair. In this case, the lacquering effect on the hair is small; it is more pronounced in the cases of examples which follow.

EXAMPLE 7 A mixture having the following composition is prepared:

Polyvinylpyrrolidune l.$ g. Urea 0.75 g. Triethanolaminu 0.75 g Ethyl alcohol 20.6 g. Colurcd polymer olexample 5 0.! g. Water q.s. for I cc When applied to white hair, this aqueous alcoholic solution leaves, after drying, a mauve shade. Shampooing of the hair thus colored immediately removes the coloration.

EXAMPLE 8 The following mixture is prepared:

Polyvinylpyrrulidone ll.8 g. Colored polymer of example 0.5 g. Hydroxycthylcnatcd lanolin 0.08 3. Alcohol q.s. for lllO cc.

20 parts of this composition are mixed with 50 parts of- Freon ll, trichlorofluoromethane and 30 parts of Freon l2, dichlorodifluotomethane, in order to bring it into the form of an aerosol. Such a product when sprayed onto the hair, leaves a mauve color which disappears completely after shampooing.

EXAMPLE 9 In the same way as in example 7, but using as polymer the product of example 1, there is obtained a mahogany coloration which disappears completely after shampooing.

EXAMPLE 10 In the same way as in example7, but using as colored polymer the product of example 4, a golden-yellow coloration is obtained which disappears after shampooing.

The present invention provides the new article of manufacture which consists of a colored resin which may be used to make hair lacquer or setting lotions, said resin being essentially characterized by the fact that it results from the simultaneous condensation of at least one alcohol and either at least one hydroxyl dye or at least one amine dye, or a mixture of these two types of dye on a polymer obtained by copolymerization of equimolecular quantities of maleic anhydride and an unsaturated monomer.

in accordance with the invention, the alcohol and the dye or dyes may be condensed on a copolymer having the following in which:

R and R" represent a hydrogen atom, a lower alkyl, a phenyl radical-or a lower alkoxy radical, and R and R" may or may not be identical; R represents either a hydrogen atom, the radical OCOCH;, the radical C N, or the radi cal COOCH n is a whole number.

Among the copolymers responding to formula I which ma be used to produce a colored polymer according to the inven tion are: copolymers of maleic anhydride and vinylalky ethers, maleic anhydride and ethylene, maleic anhydride ant vinyl acetate, maleic anhydride and alkyl acrylates o methacrylates, maleic anhydride and acrylonitrile, and others The colored polymers according to the invention may ad vantageously respond to the following general formula:

R, R, R' and n have the same significance as that hereil before indicated for formula I;

R represents a lower alkyl such as CH=, C,H,,, C,H,;

R, represents the remainder of a dye having a hydrox group;

R represents the balance of a dye comprising an amin group which may be primary or secondary nuclear or extr nuclear;

p, q and r represent whole numbers, only one of which me be 0.

Among those dyes having a hydroxyl group or a primary secondary amine group, which may be used in carrying out ti invention are; the azo, anthraquinone, azinic and amim triphenylmethane dyes, as well as dyes which are nitrophei ylenediamine derivatives.

Such dyes make it possible to obtain colorations which n. the gamut of the color spectrum, e.g. blue, violet. red, bro or yellow.

in order to obtain a desired shade several copolymers a cording to the invention having different colors may be mixr together.

It is also possible to obtain a polymer of the desired ShBt directly by condensing a suitable mixture of dyes on tl copolymer.

The properties of the colored polymers obtained in a cordance with the invention depend partly on the choice i the particular alcohol which is condensed on the colorle copolymer and partly on the proportions between the vario' dyes and the alcohol condensed on the copolymer.

The colored copolymers according to the inventit generally comprise -95 percent alcohol in proportion to tl anhydride groups of the starting polymer and 5 to 20 perce of dyes in proportion to said anhydride groups.

By neutralizing the semiesters or mixtures of semiesters at semiamides which constitute the colored copolymers accor ing to the invention with mineral or organic bases, the copolymers are rendered soluble in alcohol or in hydro: coholic solutions, a characteristic which is indispensable wh they are to be used as cosmetic resins in aerosol form or solutions.

The colored copolymers according to the invention may made by condensing the alcohol and the dye or dyes on t colorless copolymer while heating the mixture in a solve such as dioxane or the ketones.

The order in which these substances are condensed on t copolymer may be varied.

The dye may be condensed first and then the alcohol, but is also possible to condense part of the alcohol first, then t dye. and finish up by condensing the remainder of the alcoh The alcohol and dye may also be condensed simultaneously the colorless copolymer. The colored copolymer is then it lated by precipitation and identified by determination of its amide-ester or amide groups.

The condensation of the dye on the copolymer according to the invention does not otherwise alter the cosmetic properties of the colorless copolymer as compared with copolymers obtained by condensation of the same alcohol, or the same starting copolymer without any dye.

The result is a priori surprising because colored copolymers obtained by condensing a dye of the same type lead to insoluble colored resins which even when mixed in relatively small quantities with colorless resins obtained by the condensation of alcohol alone, render the latter unsuitable for use in cosmetic preparations.

Another object of the present invention is to provide hair lacquers or setting lotion characterized by the fact that they contain in an alcoholic or hydroalcoholic solution at least one colored copolymer as hereinbefore described.

In order to obtain aerosol hair lacquers according to the invention a 2 to 20 percent alcoholic solution of the colored polymer or ofa mixture ofthis colored copolymer and another cosmetic resin is first prepared. and to this solution there is added from 2 to 3 times its weight of a propellant such as those halogenated hydrocarbons sold under the trademark Freon which has been liquefied under pressure.

A setting lotion according 20 the invention may be prepared by mixing a 20-50" alcoholic solution with 0.5-6 percent by weight of a colored copolymer or a mixture of colored copolymers with other colorless copolymers.

The hereinbefore described colorless copolymers may also be used to form hair lacquers or setting lotions by mixing them with other colorless polymers such as polyvinylpyrrolidone, or copolymers of polyvinylpyrrolidone and vinyl acetate, vinyl acetate and unsaturated carboxylic acid, semiesters of copolymers of maleic anhydride and alkylvinyl ethers, in proportions dependent on the intensity of the coloration soughtv The hair lacquers and setting lotions according to the invention may also comprise any other substances conventionally used in cosmetics, such for example as placticizers or perfumes.

The hair lacquers or setting lotions made from copolymers according to the invention have the same cosmetic properties as hair lacquers or setting lotions made from colorless resins having the same compositions except for the dye.

The coloration of the resins enables them to impart a certain shade to the hair without thereby adversely affecting the other qualities of the cosmetic.

The tests carried out by applicant have shown that the colored copolymers according to the invention will not stain the skin or clothing after they have been applied to the hair.

Moreover, they may be completely and easily removed by washing or brushing so that the hair can be given a particular shade for as short a time as desired.

In order that the invention may be clearly understood, several examples of the preparation and use of these copolymers will now be described purely by way of example, without limiting the scope of the invention to the details thereof.

EXAMPLE 11 Preparation of a mixed semiester colored copolymer by condensing n-butyl alcohol and a dye having the following formula on a methylvinyl ether/maleic anhydride copolymer.

150 ml. of methylisobutylketone, 6.3 g. (0.02 moles) of the above dye, 13.3 g. (0.18 moles) of n-butanol and 30 g. (0.2 moles) of the methylvinyl ether/maleic anhydride copolymer sold as Gantrez AN 1 19" by the General Aniline & Film Corporation which has a specific viscosity of 0.1-0.5 in a l percent solution of the copolymer in methyl ethyl ketone at 25 C. is introduced into a flask provided with agitating means, a thermometer, and a reflux condenser.

By measurement of the anhydride group of this copolymer, it has been determined that the molar ratio between the methylvinyl ether and maleic anhydride is 0.9/1.

The mixture is kept at reflux for 16 hours. Esterification is completed by adding 15 grams (0.2 moles) of n-butanol and then heating the mixture to reflux for another 8 hours.

At the end of the reaction the colored copolymer is precipitated by adding ether and the uncombined dye is extracted.

After drying a 79 percent yield by weight is obtained of a red powder which after neutralization is soluble in alcohol and in a hydroalcoholic mixture.

Analyses indicate that 35 percent of the theoretically indicated quantity ofdye is combined.

EXAMPLE 12 Preparation of a mixed semiester colored copolymer by condensing n-butyl alcohol and a dye having the following formula on a methylvinyl ether/maleic anhydride copolymer:

, o Srnomcmon ml. of methylisobutylketone, 13.3 g. (0.18 moles) ofnbutanol and 30 g. (0.2 moles) of methylvinyl ether/maleic anhydride copolymer are introduced into a flask having agitating means and a thermometer and a reflux condenser.

The mixture is brought to reflux for 12 hours.

6 g. (0.02 moles) of the above dye are then added and the mixture kept at reflux for another 8 hours. The esterification is completed by adding 15 g. (0.2 moles) of n-butanol and heating to reflux for another 8 hours.

When the reaction has been completed the colored copolymer is precipitated with ether and the uncombined dye extracted.

After drying, the result is a 91 percent by weight yield ofa blue powder which, after neutralization, is soluble in alcohol and in a hydroalcoholic mixture.

Analyses show that 23 percent of the theoretically indicated quantity of dye is combined.

EXAMPLE 13 Preparation of a mixed semiester colored copolymer by condensing n-butyl alcohol and a dye having the following formula on a methylvinyl ether/maleic anhydride copolymer:

CH -CH OH NHCH:

150 ml. of methylisobutylketone, 13.3 g. (0.18 moles) of nbutanol, 4.5 g. (0.02 moles) of the above dye, and 30 g. (0.2 moles) of the copolymer of methylvinyl ether and maleic anhydride is introduced into a flask provided with agitating means, a thermometer and a condenser.

The mixture is brought to reflux for 16 hours. The esterification is completed by adding 15 g. (0.2 moles) of n-butanol and heating to reflux for an additional 8 hours.

After the reaction is over the colored copolymer is precipitated with ether and the uncombined dye extracted.

After drying. the result is a yield of 85 percent by weight of a violet powder which, after neutralization, is soluble in alcohol and in a hydroalcoholic mixture.

Analyses have shown that 40 percent of the theoretically indicated quantity ofdye is combined.

EXAMPLE l4 Preparation of a mixed semiester colored copolymer by condensing n-butyl alcohol and a dye having the following formula on the copolymer of methylvinyl ether and maleic anhydride:

The process is the same as in example ll, except that twice the amount ofdye is used. that is to say, 0.04 moles instead of 0.02 moles for each 0.2 moles ofthe colorless copolymer.

After precipitation, extraction and drying, the result is a 68 percent yield by weight of a red powder which, after neutralization, is soluble in alcohol and in a hydroalcoholic mixture.

Analyses have shown that 29 percent ofthe theoretically indicated quantity ofdye is combined.

EXAMPLE [5 Preparation of a mixed semiamide semiester colored copolymer by condensing n-butyl alcohol and a dye having the following formula on a copolymer of methylvinyl ether and maleic anhydride:

150 ml. of methylisobutylketone, 13.3 g. (0.18 moles) of nbutanol, 4 g. (0.02 moles) of the above dye and 30 g. (0.2 moles) of the methylvinyl ether/maleic anhydride copolymer are introduced into a flask provided with agitating means, a thermometer and a condenser.

The mixture is heated to reflux for H5 hours. The esterification is completed by adding g. (0.2 moles) ofn-butanol and heating to reflux for another 8 hours.

At the end of the reaction the colored copolymer is precipitated by using ether and the uncombined dye is extracted.

After drying, the result is a yield of 89 percent by weight of a yelloworange powder which, after neutralization is soluble in alcohol and in a hydroalcoholic mixture.

Analyses indicated that 86 percent of the theoretically predicted quantity of dye is combined.

EXAMPLE 16 Preparation of a mixed semiamide semiester colored copolymer by condensation of n-butyl alcohol and a dye having the following formula on a methylvinyl ether/maleic anhydride copolymer:

CH; CH;

150 ml. of methylisobutylketone, 13.3 g. (0.l8 moles) of nbutanol, 4.25 g. (0.02 moles) of the above dye, and g. of the methylvinyl ether/maleic anhydride copolymer are introduced into a flask provided with agitating means, a thermometer and a reflux condenser.

The mixture is heated to reflux for 16 hours. Esterification is then completed by adding 15 g. (0.2 moles) of n-butanol and heating for another 8 hours. The colored copolymer is precipitated at the end of the reaction and the uncombined dye is extracted.

After drying, the result is an 88 percent yield by weight ofa yellow-orange powder which after neutralization is soluble in alcohol and in a hydroalcoholic mixture.

Analyses shows that 82 percent of the theoretically predicted quantity of dye is combined.

EXAMPLE l7 Preparation of a mixed semiamide semiester colored copolymer by condensing n-butyl alcohol and a dye having the following formula on a copolymer of methylvinyl ether and maleic anhydride:

ml. of methylisobutylketone, moles of 6.65 g. (0.09 moles) of n-butanol, 3 g. (0.0] moles) of the above dye, and 15 g. (0.l moles) of the copolymer of methylvinyl ether and maleic anhydride is introduced into a flask provided with agitating means, a thennometer, and a reflux condenser.

The mixture is heated to reflux for 20 hours. Esterification is then completed by adding 7.5 g. (0.l moles) of n-butanol and heating for another 8 hours.

At the end of the reaction the colored copolymer is precipitated with ether and the uncombined dye is extracted.

After drying, the result is a yield of 87 percent by weight of a brown powder which, after neutralization, is soluble in all cohol and in a hydroalcoholic mixture.

Analyses shows that 77 percent of the theoretically predicted quantity of dye is combined.

EXAMPLE [8 In order to make a colored aerosol hair lacquer according to the invention, the following solution is first prepared:

copolymer ohtulned as indicated in example I2 I g. copolymer of vinyl acetate and crotonic acid 7 g. 2-umlno-Z-methyl-propanol q.s p. llsg.

Ethyl alcohol 100 25 grams of Freon solution is mixed in an aerosol bomb with 47 grams of trichlorofluoromethane sold under the trademark Freon ll" and 28 grams of dichlorodifluoromethane sold under the trademark Freon l2."

When this mixture is sprayed onto the hair a deep blue shade is produced but the lacquer may be removed by brushing and does not come offon pillows or linen.

EXAMPLE [9 In order to make a colored aerosol hair lacquer according to the invention, the following solution is first prepared:

(opolymer obtained as indicated in Example I l l gram (opolymer ofvinyl acetate and crotonic acid 7 gram 2-timino-Z-methyl-propanol L28 gram Ethyl alcohol q.s.p. 100 grams EXAMPLE 20 in order to make a setting lotion according to the invention, the following solution is first prepared:

Copolymer obtained as indicated in example l l 2 gram Z-amino-Z-methyl-propanol 0.72 gram ethyl alcohol 50 ml.

water qsp. lOO ml.

This solution is applied to wet auburn hair, after shampooing. The hands of the user remain completely unstained.

After conventional setting and drying a very bright copper shade is produced which will not rub off on a white towel.

EXAMPLE 2] In order to make a setting lotion in accordance with the invention, the following solution is prepared:

Copolyrner obtained as indicated in example 15 0.4 gram Copolymer obtained as indicated in example l2 0.36 gram Copolyrner obtained as indicated in example l3 1.4 gram Z-amino-Z-mcthyl-propanol q.s.p. pH 7 ethyl alcohol 50 ml. Water q.s.p. I ml.

This solution is then applied to wet blond hair after shampooing. The skin of the user remains unstained.

After conventional setting and drying a burnt mauve shade is obtained. The product does not rub off on linen, brushes or pillows.

The present invention also provides a colored resin which can be used to prepare hair lacquers or setting lotions, which resin is essentially characterized by the fact that it consists of a polymer comprising on the one hand monomers suitable for the production of cosmetic resins and, on the other hand, at least one monomer having a reactive epoxy group to which a dye is chemically bound by condensation with either its primary or secondary amine group or its hydroxyl group.

The monomers comprising an epoxy group may be for example glycidyl methacrylate, glycidyl acrylate, or allylglycidyl ether.

The monomers which may be used for obtaining cosmetic resins include vinyl esters such as vinyl acetate, vinyl lactams such as vinylpyrrolidone, alkyl acrylates or methacrylates, and acrylamides or methacrylamides whether substituted or not.

Suitable dyes which comprise a primary or secondary amine group or a hydroxyl function which may be chemically bound to the colorless copolymers by condensing with the epoxy group include the azoic dyes, and the anthraquinone dyes, as well as those which derive from the nitrophenylenediamines. Such dyes make it possible to produce blues, violets, reds, browns, or yellows.

In order to obtain the desired shade, several colored copolymers having different colors can be mixed together, or several successive dyes of different colors may be bound to the copolymer. In this case only a small quantity of the first dye is used so that sufficient epoxy groups remain on the copolymer to permit a second and even a third dye to be bound to the copolymer.

ln certain cases it may be advantageous, in accordance with the invention, to condense a dye on the colorless copolymer in less than stoichiometric proportions so as to leave epoxy groups which may improve the cosmetic qualities of the resin.

The properties of the colored polymers obtained in accordance with the invention are obviously dependent on the starting monomers as well as on the proportion in which they are mixed.

The copolymers according to the invention may for example contain from 2 to 30 percent and preferably from to percent of the monomer having the reactive epoxy group,

such as glycidyl methacrylate, glycidyl acrylate, or allylglycidyl ether.

In addition to those monomers, such as vinyl acetate, which impart a tendency toward insolubility to the resin, the copolymers according to the invention comprise, depending upon the properties desired, about 5 to 30 percent of monomers which render the resulting resin soluble in alcohol or water, an indispensable property, particularly when it is to be used in aerosol or solution form.

Vinylpyrrolidone, in the proportions indicated above, is preferably used for this purpose.

in order to prepare the hair lacquers or setting lotions, the colored copolymers according to the invention may be used alone or mixed with other colorless polymers such as polyvinylpyrrolidone or copolymers such as polyvinylpyrrolidone/vinyl acetate, in proportions which depend on the intensity of the color sought.

Another object of the present invention is to provide a colorless polymer capable of being colored by a condensation reaction with a dye having a primary or secondary amine group or a hydroxyl group, said polymer being essentially characterized by the fact that it is prepared by starting with at least one monomer having a reactive epoxy group and at least one other monomer suitable for use in preparing a cosmetic resin.

The copolymers according to the invention may be prepared according to various known processes. However, it seems preferable to carry out the polymerization in a solvent such as dioxane, dimethylformamide, or the ketones, in the presence of a catalyst such as benzoyl peroxide or diazo-isobutyronitrile.

The condensation with the epoxy group and the bonding of the dye to the resin may be carried out by heating the dye and the colorless copolymer in a solvent such as dimethylformamide, dioxane or the ketones.

It has been noted that if a dye having primary or secondary amine groups is used, it is not necessary to employ a catalyst. On the contrary when a dye comprising a hydroxyl function is used, it is best to employ a catalyst such as boron trifluoride in the form of 36 percent solution in ether.

The quantity of catalyzer may vary from 0.01 to 0.2 percent by weight of the colored copolymer,

The progress of the condensation reaction may be easily followed by measuring the progressive disappearance of the epoxy group.

It is noteworthy that the reaction of the dye on the copolymer according to the invention in no way affects the shade of the dye, or the cosmetic properties of the resulting colored resins as compared with those of the colorless starting resins.

Another object of the present invention is to provide hair lacquers or setting lotions characterized by the fact that they contain in an alcoholic or hydroalcoholic solution at least one colored copolymer of the type hereinbefore described.

In order to obtain aerosol lacquers according to the invention, it is possible for example to first prepare a 2 to 20 percent, and preferably a 4 to 12 percent solution of the colored copolymer hereinbefore described, (or a mixture of this colored copolymer and another cosmetic resin) in alcohol, and then add to this solution from 2 to 3 times its own weight of a propellent which has been liquefied under pressure, such as any of the halogenated hydrocarbons sold under the trademark Freon."

Setting lotions according to the invention may be prepared by mixing into an alcoholic solution having from 20 to 50 of alcohol about 0.5 to 6 percent, and preferably from 1 to 3 percent by weight of at least one colored copolymer such as has been described which copolymer may be mixed with other colorless cosmetic resins.

Of course, the hair lacquers and setting lotions according to the invention may comprise any other substances customarily used for cosmetic purposes, such, for example, as plasticizers or perfumes.

The hair lacquers or lotions made from colored copolymers according to the invention have the cosmetic properties of hair lacquers or setting lotions made from colorless resins hav ing the same composition, except for the dye.

The color of the resins makes it possible for them to impart to the hair a certain shade without any deterioration in its other cosmetic properties.

Moreover, resins according to the invention are completely and easily removed by washing or brushing, so that the hair may be given a certain particular shade or color for as short a time as may be desired.

In order that the invention may be more clearly understood several examples will now be described. without limiting the scope of the invention to the details thereof.

EXAMPLE 22 Preparation of copolymer comprising 70 percent vinyl acetate, 25 percent vinylpyrrolidone and percent glycidyl methacrylate:

The following monomers are introduced into a flask provided with an agitator, a condenser, a thermometer, and a tube for introducing nitrogen:

Vinyl acetate Ht) 5 Vrnylpy rrolidone Sll g Glycldyl mclhacrylate l0 3 300 g. of dioxane and 3 g. of diazo-isobutyronitrile are added, and the mixture heated to reflux for 24 hours. After cooling the copolymer is precipitated with ether, and dried.

A 95 percent yield of a white powder is obtained. said powder having an epoxy index corresponding to the polymerization of4.5 percent ofthe glycidyl methacrylate.

EXAMPLE 23 Preparation of a copolymer comprising 70 percent vinyl acetate, 25 percent vinylpyrrolidone and 5 percent allylglycidyl ether:

The procedure is the same as in example 22, except that the glycidyl methacrylate is replaced by allylglycidyl ether.

The result is a 95 percent yield of a colorless copolymer having an epoxy index corresponding to the polymerization of 3.8 percent ofthe allylglycidyl ether.

EXAMPLE 24 Coloring of the copolymer described in example 22 by condensing its epoxy groups with l,4-diamino anthraquinone having the formula:

g. of the copolymer described in example 22, 4.4 g. of the above dye, and 50 g. ofdimethylformamide are introduced into a flask provided with agitating means, a thermometer, and a reflux condenser. The quantity of dye introduced is double the theoretical amount.

The mixture is heated to 100C. for IS hours while keeping track of the evolution of the condensation by means of the epoxy index. At the end of the reaction the polymer is precipitated, the uncombined dye removed, and the polymer dried.

The result is a 70 percent yield ofa violet colored powder, which is soluble in alcohol and in a hydroalcoholic mixture. lt was found that 75 percent of the epoxy groups have been condensed with the dye.

EXAMPLE 2s Coloring of the copolymer described in example 22 by con densing its epoxy groups with amino-azobenzene having the formula:

Thirty grams ofthe copolymer described in example 22, 3.6 g. of the above dye, and 50 g. of dimethylformamide are introduced into a flask provided with agitating means, a thermometer. and a reflux condenser. The amount of dye is double the theoretical quantity.

The mixture is heated to 100 C. for l2 hours. When the reaction ends, the copolymer is precipitated. the dye which remains uncombined is extracted, and the copolymer dried.

The result is an overall yield of 75 percent of a yelloworange powder. which is soluble in alcohol and in a mixture of water and alcohol. 96 percent of the epoxy groups have been condensed.

EXAMPLE 26 Coloring of the copolymer described in example 22 by condensing its epoxy groups with Organol" brown having the 30 g. of the copolymer described in example 22, 8.6 g. of the above dye, and 75 g. of dioxane are introduced into the flask. The quantity of dye is twice the theoretical amount.

The mixture is heated to 100 C. for 14 hours after which the polymer is precipitated, the excess dye extracted and the polymer dried.

The result is an overall yield of percent ofa red maroon powder, soluble in a mixture of water and alcohol and in alcohol. percent ofthe epoxy groups have been condensed.

The resulting colored resin absolutely will not stain either the skin or the clothing.

EXAMPLE 27 Coloring the copolymer described in example 22 by condensing its epoxy groups with the dye sold as "Celliton RN" by BASE and having the formula:

30 g. of the copolymer described in example 22, 6.6. g. of the above dye, 60 g. of dimethylformamide and 0.3 g. of boron fluoride are placed in a flask. The quantity of dye is double the theoretical amount.

The mixture is heated to l00 C. for 16 hours. The polymer is then precipitated, the excess dye removed, and the polymer dried.

The resulting copolymer, which is obtained with a yield of 7l percent is a violet-red powder soluble in alcohol and in a mixture of water and alcohol.

percent of the epoxy groups were found to have been condensed with the dye.

CHzCH OH EXAMPLE 28 Coloring of the copolymer described in example 22 by condensing its epoxy groups with a dye having the formula:

CH3 11.7. q. tln,cmuu

30 g. of the copolymer described in example 22, together with 2.4 g. of the above dye, 50 g. of dimethylformamide and 0.2 g. of boron trifluoride are heated to 100 C. for 15 hours. The amount of dye is 10 percent in excess of the equimolecular quantity.

The polymer is precipitated, the excess dye extracted. and the polymer dried.

This results in a yield of 60 percent of a violet powder which is soluble in alcohol and in a mixture ofwater and alcohol.

It was found that lOO percent ofthe epoxy groups were condensed with the dye.

EXAMPLE 29 Coloring of the copolymer described in example 23 by com densing its epoxy groups with the brown Organol" dye having the formula:

EXAMPLE 30 Coloring of the copolymer described in example 23 by condensing its epoxy groups with a dye having the formula:

CgHs

30 g. of the copolymer described in example 23, together with 3.45 g. of the above dye, 45 g. of pure methylethylketone and 0.03 g. of boron trifluoride are placed in a flask.

The quantity of dye is 10 percent in excess of the equimolecular quantity.

The mixture is heated to reflux for l4 hours while checking the progress ofthe condensation by means of the epoxy index.

The polymer is then precipitated, the uncombined dye is extracted and the polymer is dried.

The result is a yield of 84 percent ofa red powder which is soluble in alcohol and in a hydroalcoholic mixture.

Testing shows that 100 percent of the epoxy groups have been condensed with the dye.

EXAMPLE 3i Coloring the copolymer described in example 23 by condensing its epoxy groups with the scarlet dye sold as Cibacet 2 B" and having the formula:

1 O NHCHgCHgOIi 30 g. of the copolymer described in example 23, together with 3.45 g. of the above dye, 45 g. of pure methylethylketone and 0.03 g. of boron trifiuoride are placed in a flask.

The quantity of dye is l0 percent in excess of the equimolecular quantity.

The mixture is heated to reflux for l4 hours while checking the progress of the condensation by means of the epoxy index.

The polymer is then precipitated, the uncombined dye is extracted and the polymer is dried.

The result is a yield of 84 percent ofa red powder which is soluble in alcohol and in a hydroalcoholic mixture.

Testing shows that l00 percent of the epoxy groups have been condensed with the dye.

EXAMPLE 32 In order to prepare a colored aerosol hair lacquer, the following soiution is prepared:

Copolymcr described in example 29 8 g. copolymer described in example 23 4 g. Ethyl alcohol q.s.p. I00 g 25 g. of this solution is introduced into an aerosol bomb together with 48 g. of trichlorofluoromethane sold under the trademark Freon ll and 28 g. of dichlorodifluoromethane sold under the trademark Freon 12."

This solution, when sprayed onto chestnut hair, 50 percent of which has turned white, gives a slight ash-chestnut appearance with good camouflage of the white hair.

EXAMPLE 33 in order to prepare a setting lotion, the following solution is prepared first:

copolymer described in example 2h 2 g. Ethyl alcohui 50 ml. Water qsp ml.

When this solution is used to set deep blond hair the completed coiffure has a violet rose appearance. The solution will not stain the hands while it is being applied.

EXAMPLE 34 The following solution is prepared:

Copolymer described in example 30 3 96 alcohol 50 cc. Water, q.s.pv 100 cc When this solution is applied as a setting lotion to chestnut hair the coiffure. when dried, has a bluish appearance.

EXAMPLE 35 The following solution is prepared:

(opolymerdescribed in example 24 3 g. (opolymerdescribed in example 23 5 g polyvinylpyrrolidone l g. 96 alcohol 50 cc. Water, q.s.p. 100 cc.

45 g. of trichlorofluoromethane sold under the trademark Freon ll and 30 g. of dichlorodifluoromethane sold under the trademark "Freon 12" are added to 25 g. of this solution and the resulting mixture introduced into an aerosol bomb.

When sprayed on ordinary chestnut hair, a violet glint results.

Another one of the objects of the present invention is to provide a colored resin which can be used to prepare hair lacquers or setting lotions, which resin is essentially characterized by the fact that it consists of a copolymer comprising, on the one hand, monomers suitable for making cosmetic resins and on the other hand, at least one monomer comprising a reactive chlorine group to which at least one dye is chemically bound by quaternization of its tertiary amine group.

The monomers comprising a reactive chlorine group may be for example, vinyl chloroacetate, or N-allyl-chloroacetamide.

Other monomers which may be used in the manufacture of cosmetic resins are for example, the vinyl esters such as vinyl acetate, vinyl lactams such as vinylpyrrolidone, the alkyl acrylates and methacrylates, acrylamides or methylacrylamides, whether substituted or not, or unsaturated carboxylic acids, such as crotonic acid, acrylic acid, methacrylic acid, or itaconic acid.

Among the dyes which may be used to carry out the invention are those having a tertiary amine group capable of becoming chemically bonded by quaternization to polymers having a reactive chlorine component; the azo dyes, the anthraquinone dyes, the azinic dyes, as those dyes derived from nitrophenyldiamines and those derived from quinolines.

Dyes yielding blue, red, brown, and yellow may be selected from such dyes having a tertiary amine group.

In order to obtain a desired shade several differently colored copolymers may be mixed together, but it is also possible to bond several dyes of various colors to a single originally colorless copolymer of the type according to the invention. in this case, the first dye is used in a proportion so small that some of the reactive chlorine groups on the polymer remain uncombined, so that a second and even a third dye may then be added.

The properties of the colored copolymers naturally depend on the choice of starting monomers as well as on the proportions in which said monomers are mixed.

The copolymers according to the invention may contain, for example, from 3 to 30 percent and preferably from 5 to percent of vinyl chloroacetate of N-allyl-chloroacetamide.

In addition to the monomers such as vinyl acetate which tend to render the copolymer insoluble, the polymers according to the invention comprise, depending on the properties sought, about 5 to 30 percent of such monomers as vinylpyrrolidone or unsaturated carboxylic acids neutralized by mineral or organic bases, which render the resulting resin soluble in alcohol or hydroalcoholic mixtures, as is indispensable, especially when the resin is to be used as an aerosol or in solution.

The colored copolymers according to the invention may, when incorporated into hair lacquers or setting lotions, be used singly or in mixtures in various proportion with other colorless copolymers such as a mixture of polyvinylpyrrolidone and vinyl acetate, or a mixture of polyvinylpyrrolidone or vinyl acetate with an unsaturated acid such as crotonic acid, depending on the intensity of the coloration sought.

Another object of the present invention is the new article of manufacture which consists of a colorless polymer which is capable of being colored by quaternization with a dye having a tertiary amine group, said polymer being essentially characterized by the fact that it is made from at least one monomer having a reactive chlorine group and at least one other monomer suitable for use in manufacturing cosmetic resins.

These colorless copolymers may, for example, be polymerized when in solution with a low molecular weight alcohol such as ethyl alcohol or isopropyl alcohol, in the presence of a catalyst such as benzoyl peroxide or diazo-isobutyronitrile.

The quaternization of the colorless copolymer by the dye is brought about by heating it in a solvent, such as dioxane, acetonitrile, or a low molecular weight alcohol. The colored copolymer is isolated by precipitation and tested by measurement of the ionized chlorine.

it has been noted that condensation of the dye on the copolymer in accordance with the invention does not otherwise affect the cosmetic properties of the colorless copolymers.

Another object of the present invention is the new articles of manufacture which consist of hair lacquers or setting lotions essentially characterized by the fact that they contain in alcoholic or hydroalcoholic solution at least one colored copolymer as hereinbefore defined.

In order to produce aerosol hair lacquers according to the invention, it is possible to begin by making up a 2 to 20 percent, and preferably a 4 to 12 percent solution in alcohol of the hereinbefore described colored copolymer or of a mixture of this colored copolymer and another cosmetic resin, after which two or three times its own weight of a propellant which has been liquefied under pressure, such as one or more of the halogenated hydrocarbons sold under the trademark "Freon," is added.

A setting lotion according to the invention may be prepared by mixing in a 20 to 50 alcoholic solution about 0.5 to 6 percent and preferably 1 to 3 percent by weight of a colored copolymer, or a mixture of colored copolymers with other colorless resins.

Of course, the hair lacquers and setting lotions according to the invention may also contain other substances conventionally included in cosmetic products such, for example, as plasticizers and perfumes.

The hair lacquers or setting lotions made from colored copolymers according to the invention have the same cosmetic properties as those made from colorless resins having the same composition, except for the presence of the dye. The coloration of the resins enables them to impart a certain shade to the hair without thereby causing any deterioration in the other qualities of the cosmetic product.

Tests made by the applicant have shown that the colored copolymers according to the invention do not stain the skin or any clothing with which they may come in contact after having been applied to the hair.

Moreover, these copolymers may be completely and easily eliminated by washing or brushing the hair, so that the coiffure may be given a particular shade for as short a time as may be desired, without adversely affecting the mechanical properties of the hair.

In order that the invention may be more clearly understood, several examples will now be described, purely by way of illustration, without limiting the scope of the invention to the details thereof:

EXAMPLE 36 Preparation of a colorless copolymer comprising 70 percent vinyl acetate, 20 percent vinylpyrrolidone and I0 percent N- allyl-chloroacetamide.

The monomers are introduced into a flask provided with an agitator, a reflux condenser, a thermometer, and a tube for ad mitting nitrogen:

Vinyl acetate 70 g. Vinylpyrrolidone 20 g. N-allyl-chloroacetamidc l0 g.

220 g. of absolute ethyl alcohol and 5 g. of diazoisobutyronitrile are added and the mixture is heated to reflux for 20 hours.

After cooling, ether is used to precipitate the copolymer, with a 75 percent yield resulting.

Analysis Calculated Found Organic Cl 2.65% 2.53%

which corresponds to condensation of percent of the condensed reactive monomer.

EXAMPLE 37 Preparation of a copolymer comprising 60 percent vinyl acetate 20 percent vinylpyrrolidone and 20 percent N-allylchloroacetamide.

The same process is used under the same conditions as those described in example 36, except that the concentration of N-allyl-chloroacetamide is 20 percent instead of ll) percent.

A 70 percent yield of the copolymer sought is secured by precipitation with ether. The copolymer is in the form of a white powder.

Analysis Calculated Found Organic Cl 5.11

which corresponds to a 92.4 percent condensation of the chlorinated monomer.

EXAMPLE 38 Preparation of a copolymer comprising 70 percent vinyl acetate, 20 percent vinylpyrrolidone and percent vinyl chloroacetate.

The same process is used under the same conditions as those described in example 36, except that the N-allyichloroacetate is replaced by the vinyl chloroacetate.

After precipitation and drying a 70 percent yield of the desired copolymer is obtained Analysis Calculated Found Organic Cl 2.95! 2.78%

which corresponds to a 94 percent condensation of the chlorinated monomer.

EXAMPLE 39 Quaternization of the copolymer of example 36, using a 1,4- dihydroxy-('y-piperidino-propyl)-2-aminoanthraquinone dye having the formula:

0 0H l l CHrCH NH(CH2)a-N /CH:

CHI-CH ll l O OH Analysis Calculated Found Ionized Cl Lllk l.7%

The percentage of quaternization increases to 94 percent.

EXAMPLE 40 Quaternization of the copolymer of example 36 with a L4- diamino-(y-diethylaminopropyl)-5-aminoanthraquinone dye having the formula:

20 g. of the copolymer according to example 36 is heated to reflux with 5.2 g. of the above dye. while keeping track of the ionized chlorine being formed. After 30 hours of reflux the colored copolymer is precipitated, excess dye extracted with ether, and the copolymer dried.

A yield of 74 percent by weight of a blue powder, which is soluble in alcohol, or in a hydroalcoholic medium, is obtained.

Analysis Calculated Fun nd The percentage ofquaternization is 82 percent.

EXAMPLE 4| Quaternization of the copolymer of example 36 with a 2- amino-4-nitro-(y-diethylaminopropyl)aminobenzene dye having the formula:

[5 g. of the copolymer according to example 36, together with 2.84 g. of the above nitrated dye and 50 cc. of dioxane is placed in a flask.

The mixture is heated to reflux for 35 hours, while keeping track of the formation of ionized chlorine. The copolymer is then precipitated, subjected to extraction with ether, and dried. The result is a yellow powder, soluble in alcohol.

Analysis Calculated Found which corresponds to percent quatemization.

21 22 EXAMPLE 42 EXAMPLE 44 Quaternization of the copolymer of example 37 with a 1,4- Quatemization of the copolymer of example 36 with a 2,4- dihydroxy-(y-piperidinopropyl )-2-aminoanthraquinone dye dihydroxy-3-phenylazoquinoline dye having the formula: having the fonnula: 5

OH 1 (ll (11 b I v y -,-Nll(ClI );-N )cu, a g F ll -Lll, (Hi1 Q l g. of the copolymer described in example 36 and 2.86 g.

15 of the above dye (which corresponds to the quantity of chlorine in the copolymer) are introduced into a flask. 50 cc. of dioxane is added and the mixture heated to reflux for 24 hours.

After cooling the colored copolymer is precipitated, subjected to extraction with ether, and dried.

A yield of 83 percent by weight of a yellow powder is obtained. This powder is soluble in alcohol and in a hydroalcoholic mixture.

15 g. of the copolymer described in example 37 and 7.8 g. of the above dye (which corresponds to the quantity of organic chlorine contained in the copolymer) are introduced into a flask. 90 cc. of dioxane is added and the mixture heated to reflux. 2

After 36 hours of heating, the colored copolymer is precipitated, subjected to extraction with ether, and dried.

An 84 percent yield by weight ofa cyclamen red powder is obtained. The powder is soluble in alcohol and in a hydroalcoholic mixture. 25

Analysis Calculated Found Analysis Calculated Found kmilcd C 2.201 L16;

Ionized c1 3.22s 2.54;

which corresponds to 80 percent quaternization.

which corresponds to 78.8 percent quaternization. EXAMPLE 45 EXAMPLE 43 The following solution is prepared:

Quaternization of the copolymer of example 38 with a 1,4- Cupolymerdcscrihcd in cxumple .w 5 g diamino-(y-diethylaminopropyl)-5-aminoanthraquinone dye :W described n Example 40 3 8 ha ing the formu [:thyl alcohol qsp. I00 5 25 g. of this solution is treated with g. of

trichlorofluoromethane sold under the trademark Freon l l 0 NH, and 30 g. of dichlorodifluoromethane sold under the trade- 45 mark Freon l2" when this is sprayed onto the hair, a black tulip" sheen is obtained.

EXAMPLE 46 The following solution is prepared:

| (91103 Copolymer described in exam le 40 8 g. N Polyvinylpyrrolidone 5 g. Ethyl alcohol q.s.p. I00 g. CgH5 C 115 25 g. of this solution is treated with 48 g. of trichlorofluoromethane sold under the trademark Freon l l and 28 g. ofFreon l 2."

This composition gives a deep blue sheen when applied to dark chestnut hair. If the hair is white, it is colored bright blue.

20 g. of the copolymer described in example 38 and 5.73 g. of the above anthraquinone dye (which corresponds to the quantity of chlorine in the copolymer) is introduced into a flask. 80 cc. of dioxane are added and brought to reflux. EXAMPLE 47 After heating for 24 hours, the copolymer IS precipitated, I subjected to extraction, and dried. The followmg soluno" prepared:

A yield of 80 percent by weight of a blue powder is obtained. This powder is soluble in alcohol and in a hydroal- 'l f 39 copolymer described In example 36 lg. cohohc mlxture' Triethanolamine q.s.p. pH 7 Ethyl alcohol 50 cc. Water q.s.p. I00 cc.

Analysis When this solution is applied to chestnut hair in a setting lotion, the hair, when dried, has a violine sheen and holds the Ionized c 2.1% wave well. The solution does not stain the hands.

What is claimed is: l. A composition for coloring human hair comprising a which corresponds to 80 percent quaternization. solution of a hair coloring amount of a colored polymer and a solvent therefor. said solvent being selected from the group consisting of alcohol and aqueous alcohol solution, said polymer having the formula wherein R' is selected from the group consisting of hydrogen and methyl, R is selected from the group consisting of arylene and arylene substituted with nitro, R and R" each independently represent a member selected from the group consisting of hydrogen, methyl and B-diethylaminoethyl. and n is equal to 1 1-1 so that the molecular weight of said polymer ranges between l,000-l0,000.

2. The composition of claim 1 wherein said polymer is polyacrylyl-nitroparaphenylenediaminc.

3. The composition of claim 1 wherein said polymer is polyac rylyll -methylamino-2-nitro-4-aminobenzene.

4. The composition of claim 1 wherein said polymer is polyacrylyll -methyl-amino-2-nitro-4(B-diethylaminoethyl) aminobenzene.

5. The composition of claim 1 wherein said polymer is polyacrylyll -nitro-3-amino-4-(B- diethylaminoethyl)aminobenzene.

6. The composition of claim 1 wherein said polymer is polyacrylyl-l .4-diaminoanthraquinone.

7. A pressurized sprayable aerosol composition for coloring human hair comprising a solution of a hair coloring amount of a colored polymer and a solvent therefor; said solvent being alcohol, said polymer having the formula wherein R is selected from the group consisting of hydrogen and methyl, R is selected from the group consisting of arylene and arylene substituted with nitro. R and R each independently represent a member selected from the group consisting of hydrogen, methyl and B-diethylaminoethyl. and n is equal to 1 1-1 10 so that the molecular weight of said polymer ranges between LOCO-10,000, said colored copolymer being present in amounts of about 2-20 weight percent of the solution of colored polymer and solvent, and a halogenated hydrocarbon aerosol propellant in amounts ranging-from about 2-3 times the weight of said solution of colored polymer and solvent.

8. A composition for coloring human hair comprising a solution of a colored polymer and a solvent therefor, said solvent being selected from the group consisting of alcohol and aqueous alcohol solution, said colored polymer consisting essentially of an equimolecular methyl vinyl ether-maleic anhydride copolymer having a specific viscosity of 0.1-0.5 in a 1 percent solution of the copolymer in methylethyl ketone at 25 C. and having condensed on the anhydride group of said copolymer( 1 a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a radical directly attached to the aromatic nucleus of said dye and having the formula wherein R, and R, are each independently selected from the group consisting of hydrogen. CH C,H, and CH,CH,OH. the quantity of said dye combined with said copolymer by condensation of the anhydride group ranging between 5-20 percent and (2) a lower alltanol, the quantity of lower alkanol combined with said copolymer by condensation of the anhydride group ranging between -95 percent, said colored copolymer being present in amounts of about 05-20 percent based on the weight of said composition.

9. The composition of claim 8 wherein the dye has the formula 10. The composition of claim 8 wherein the dye has the formula 11. The composition of claim 8 wherein the dye has the for- 12. A pressurized sprayable aerosol composition for coloring human hair comprising a solution of a colored polymer and alcohol. said colored copolymer consisting essentially of an equimolecular methyl vinyl ether-maleic anhydride copolymer having a specific viscosity of 0. 1-05 in a 1 percent solution of the copolymer in methylethylketone at 25 C. and having condensed on the anhydride group of said copolymer l) a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a radical directly attached to the aromatic nucleus of said dye and having the formula wherein R and R are each independently selected from the group consisting of hydrogen, CH C H and CH,CH,OH, the quantity of said dye combined with said copolymer by condensation of the anhydride group ranging between 5-20 percent and (2) a lower alkanol, the quantity of lower alkanol combined with said copolymer by condensation of the anhydride group ranging between 80-95 percent, said colored polymer being present in amounts of about 2-20 weight percent of the solution of colored polymer and alcohol, and a halogenated hydrocarbon aerosol propellant present in amounts ranging from about 2-3 times the weight of said solution of colored polymer and alcohol.

13. A composition for coloring human hair comprising a solution of a colored polymer and a solvent therefor, said solvent being selected from the group consisting of alcohol and aqueous alcohol solutions. said colored polymer consisting essentially of 2-30 weight percent of a first monomer containing a reactive epoxy group and being selected from the group consisting of glycidyl methacrylate, glycidyl acrylate and allylglycidyl either, 5-30 weight percent of a second comonomer consisting of vinylpyrrolidone, the remaining comonomer being essentially vinyl acetate, and a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a radical directly attached to the aromatic nucleus of said dye, said radical being selected from the group consisting of:

formula 15. The composition of claim 13 wherein the dye has the formula 16. The composition of claim 13 wherein the dye has the formula 17. The composition of claim 13 wherein the dye has the formula CHzCHzOH 18. The composition of claim 13 wherein the dye has the formula fl) IIIHCH;

ll 1 o NHcmomoH 19. The composition of claim 13 wherein the dye has the formula CaHs 20. The composition of claim 13 wherein the dye is 1,4- diaminoanthraquinone.

21. A pressurized sprayable aerosol composition for coloring human hair comprising a solution of a colored polymer and a solvent selected from the group consisting of alcohol and aqueous alcohol. said colored polymer consisting essentially 012-30 weight percent of a first monomer containing a reactive epoxy group and being selected from the group consisting of glycidyl methacrylate. glycidyl acrylate and allylglycidyl ether, 5-30 weight percent of a second comonomer consisting of vinylpyrrolidone, the remaining comonomer being essentially vinyl acetate. and a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a radical directly attached to the aromatic nucleus of said dye, said radical being selected from the group consisting of:

and

wherein R, and R are selected from the group consisting of hydrogen, CH C H and C.H,,, with the proviso in (a) that at least one of R, and R is hydrogen, the quantity of said dye combined with said copolymer by condensation of the epoxy group ranging between -100 percent of theoretical, said colored polymer being present in amounts ranging from 2-20 weight percent of the solution of colored polymer and solvent and a halogenated hydrocarbon propellant present in amounts ranging from about 2-3 times the weight of said solution of colored polymer and solvent.

22. A composition for coloring human hair comprising a solution ofa colored polymer and a solvent therefor, said solvent being selected from the group consisting of alcohol and aqueous alcohol solutions, said colored polymer consisting essentially of 3-30 weight percent ofa first comonomer containing reactive chlorine and selected from the group consisting of vinyl chloroacetate and N-allyl-chloroacetamide, 5-30 weight percent of a second comonomer consisting of vinylpyrrolidone, the remaining comonomer being essentially vinyl acetate, and a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a tertiary amine group, the quantity of said dye combined with said copolymer by quatemization of the tertiary amine group ofsaid dye ranging between ab0ut78.8 to about 94 percent of theoretical said colored polymer being present in said composition in amounts ranging from about 05-20 percent based on the weight of said composition.

23. The composition of claim 22 wherein said dye is 1,4- dihydroxy-Z-(-y-piperidinopropyl)aminoanthraquinone.

24. The composition of claim 22 wherein said dye is l,4- diamino-S-(y-diethylaminopropyl)aminoanthraquinone.

25. The composition of claim 22 wherein said dye is 2- amino-4-nitr0-('y-diethylaminopropyl)aminobenzene.

26. The composition of claim 22 wherein said dye is 2,4- dihydroxy-3-phenylazoquinoline.

27. A pressurized sprayable aerosol composition for coloring human hair comprising a solution of a colored polymer and alcohol, said colored polymer consisting essentially of 3-30 weight percent of a first comonomer containing reactive chlorine and selected from the group consisting of vinyl chloroacetate and N-allyl-chloroacetamide, 5-30 weight percent of a second comonomer consisting of vinylpyrrolidone, the remaining comonomer being essentially vinyl acetate, and a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a tertiary amino group, the quantity of said dye combined with said copolymer by quatemization of the tertiary amine group of said dye ranging between about78.8 to about 94 percent of theoretical, said colored polymer being present in amounts ranging from 2-20 weight percent of the solution of colored polymer and alcohol and a halogenated hydrocarbon propellant present in amounts ranging from about 2-3 times the weight of said mixture of colored polymer and alcohol. 

2. The composition of claim 1 wherein said polymer is polyacrylyl-nitroparaphenylenediamine.
 3. The composition of claim 1 wherein Said polymer is polyacrylyl-1-methylamino-2-nitro-4-aminobenzene.
 4. The composition of claim 1 wherein said polymer is polyacrylyl-1-methyl-amino-2-nitro-4( Beta -diethylaminoethyl) aminobenzene.
 5. The composition of claim 1 wherein said polymer is polyacrylyl-1-nitro-3-amino-4-( Beta -diethylaminoethyl)aminobenzene.
 6. The composition of claim 1 wherein said polymer is polyacrylyl-1,4-diaminoanthraquinone.
 7. A pressurized sprayable aerosol composition for coloring human hair comprising a solution of a hair coloring amount of a colored polymer and a solvent therefor, said solvent being alcohol, said polymer having the formula
 8. A composition for coloring human hair comprising a solution of a colored polymer and a solvent therefor, said solvent being selected from the group consisting of alcohol and aqueous alcohol solution, said colored polymer consisting essentially of an equimolecular methyl vinyl ether-maleic anhydride copolymer having a specific viscosity of 0.1-0.5 in a 1 percent solution of the copolymer in methylethyl ketone at 25* C. and having condensed on the anhydride group of said copolymer (1) a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a radical directly attached to the aromatic nucleus of said dye and having the formula wherein R1 and R2 are each independently selected from the group consisting of hydrogen, CH3, C2H5 and CH2CH2OH, the quantity of said dye combined with said copolymer by condensation of the anhydride group ranging between 5-20 percent and (2) a lower alkanol, the quantity of lower alkanol combined with said copolymer by condensation of the anhydride group ranging between 80-95 percent, said colored copolymer being present in amounts of about 0.5-20 percent based on the weight of said composition.
 9. The composition of claim 8 wherein the dye has the formula
 10. The composition of claim 8 wherein the dye has the formula
 11. The composition of claim 8 wherein the dye has the formula
 12. A pressurized sprayable aerosol composition for coloring human hair comprising a solution of a colored polymer and alcohol, said colored copolymer consisting essentially of an equimolecular methyl vinyl ether-maleic anhydride copolymer having a specific viscosity of 0.1-0.5 in a 1 percent solution of the copolymer in methylethylketone at 25* C. and having condensed on the anhydride group of said copolymer (1) a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a radical directly attached to the aromatic nucleus of said dye and having the formula wherein R1 and R2 are each independently selected from the group consisting of hydrogen, CH3, C2H5 and CH2CH2OH, the quantity of said dye combined with said copolymer by condensation of the anhydride group ranging between 5-20 percent and (2) a lower alkanol, the quantity of lower alkanol combined with said copolymer by condensation of the anhydride group ranging between 80-95 percent, said colored polymer being present in amounts of about 2-20 weight percent of the solution of colored polymer and alcohol, and a halogenated hydrocarbon aerosol propellant present in amounts ranging from about 2-3 times the weight of said solution of colored polymer and alcohol.
 13. A composition for coloring human hair comprising a solution of a colored polymer and a solvent therefor, said solvent being selected from the group consisting of alcohol and aqueous alcohol solutions, said colored polymer consisting essentially of 2-30 weight percent of a first monomer containing a reactive epoxy group and being selected from the group consisting of glycidyl methacrylate, glycidyl acrylate and allylglycidyl ether, 5-30 weight percent of a second comonomer consisting of vinylpyrrolidone, the remaining comonomer being essentially vinyl acetate, and a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a radical directly attached to the aromatic nucleus of said dye, said radical being selected from the group consisting of: wherein R1 and R2 are selected from the group consisting of hydrogen, CH3, C2H5 and C4H9, with the proviso in (a) that at least one of R1 and R2 is hydrogen, the quantity of said dye combined with said copolymer by condensation of the epoxy group ranging between 75-100 percent of theoretical, said polymer being present in said composition in amounts ranging from about 0.5-20 percent based on the weight of said composition.
 14. The composition of claim 13 wherein the dye has the formula
 15. The composition of claim 13 wherein the dye has the formula
 16. The composition of claim 13 wherein the dye has the formula
 17. The composition of claim 13 wherein the dye has the formula
 18. The composition of claim 13 wherein the dye has the formula
 19. The composition of claim 13 wherein the dye has the formula
 20. The composition of claim 13 wherein the dye is 1,4-diaminoanthraquinone.
 21. A pressurized sprayable aerosol composition for coloring human hair comprising a solution of a colored polymer and a solvent selected from the group consisting of alcohol and aqueous alcohol, said colored polymer consisting essentially of 2-30 weight percent of a first monomer containing a reactive epoxy group and being selected from the group consisting of glycidyl methacrylate, glycidyl acrylate and allylglycidyl ether, 5-30 weight percent of a second comonomer consisting of vinylpyrrolidone, the remaining comonomer being essentially vinyl acetate, and a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a radical directly attached to the aromatic nucleus of said dye, said radical being selected from the group consisting of: wherein R1 and R2 are selected from the group consisting of hydrogen, CH3, C2H5 and C4H9, with the proviso in (a) that at least one of R1 and R2 is hydrogen, the quantity of said dye combined with said copolymer by condensation of the epoxy group ranging between 75-100 percent of theoretical, said colored polymer being present in amounts ranging from 2-20 weight percent of the solution of colored polymer and solvent and a halogenated hydrocarbon propellant present in amounts ranging from about 2-3 times the weight of said solution of colored polymer and solvent.
 22. A composition for coloring human hair comprising a solution of a colored polymer and a solvent therefor, said solvent being selected from the group consisting of alcohol and aqueous alcohol solutIons, said colored polymer consisting essentially of 3-30 weight percent of a first comonomer containing reactive chlorine and selected from the group consisting of vinyl chloroacetate and N-allyl-chloroacetamide, 5-30 weight percent of a second comonomer consisting of vinylpyrrolidone, the remaining comonomer being essentially vinyl acetate, and a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a tertiary amine group, the quantity of said dye combined with said copolymer by quaternization of the tertiary amine group of said dye ranging between about78.8 to about 94 percent of theoretical said colored polymer being present in said composition in amounts ranging from about 0.5-20 percent based on the weight of said composition.
 23. The composition of claim 22 wherein said dye is 1,4-dihydroxy-2-( gamma -piperidinopropyl)aminoanthraquinone.
 24. The composition of claim 22 wherein said dye is 1,4-diamino-5-( gamma -diethylaminopropyl)aminoanthraquinone.
 25. The composition of claim 22 wherein said dye is 2-amino-4-nitro-( gamma -diethylaminopropyl)aminobenzene.
 26. The composition of claim 22 wherein said dye is 2,4-dihydroxy-3-phenylazoquinoline.
 27. A pressurized sprayable aerosol composition for coloring human hair comprising a solution of a colored polymer and alcohol, said colored polymer consisting essentially of 3-30 weight percent of a first comonomer containing reactive chlorine and selected from the group consisting of vinyl chloroacetate and N-allyl-chloroacetamide, 5-30 weight percent of a second comonomer consisting of vinylpyrrolidone, the remaining comonomer being essentially vinyl acetate, and a dye selected from the group consisting of azo, anthraquinone and nitrophenylenediamine dyes containing a tertiary amino group, the quantity of said dye combined with said copolymer by quaternization of the tertiary amine group of said dye ranging between about78.8 to about 94 percent of theoretical, said colored polymer being present in amounts ranging from 2-20 weight percent of the solution of colored polymer and alcohol and a halogenated hydrocarbon propellant present in amounts ranging from about 2-3 times the weight of said mixture of colored polymer and alcohol. 